Studies of vanadium complexes in sulfur-rich ligation environment

• Main Authors: Yi-FangTsai, 蔡宜芳
• Other Authors: Hua-Fen Hsu
• Format: Others
• Language: en_US
• Published: 2010
• Online Access: http://ndltd.ncl.edu.tw/handle/50141729701567470103

博士 === 國立成功大學 === 化學系碩博士班 === 98 === In our efforts to understand the chemistry of vanadium complexes in S-rich ligation environment, we have utilized PS2 ligands (PS2= PhPS2H, PhPS2” and tBuPS2H), PS1 ligands (PS1= PS1H, PS1’ and PS1”), and SiS3 ligands (SiS3 =MeSiS3H and HSiS3’) to react with vanadium ion. The reactions led to the formation of three types of vanadium thiolate compounds. They are non-oxo monuclear VIII/IV thiolate complexes, dinuclear oxo VIV thiolate complexes and multinuclear VIII/IV thiolate clusters. The isolated compounds for the first type are [VIII(PhPS2H)2]-(I-1), [VIII(PhPS2”)2]-(I-2), [VIII(tBuPS2H)2]- (I-3), [VIV(PhPS2H)2] (I-4), [VIV(PhPS2”)2] (I-5), [VIII(PS1H)3] (I-6),[VIII(PS1’)3] (I-7), [VIII(PS1”)3] (I-8). Complexes I-1 – I-5 have P2S4 donor set and complexes I-6 – I-8 have P3S3 ligantion environment. The geometries adopted for most of these compounds should be considered between two limits, octahedron and trigonal prism, according to their structural parameters. Exceptional one is complex I-5 that has a geometry closed to an ideal trigonal prism. In the second type, we reported two dinuclear oxo VIV thiolate complexes, [VIVO(CH3)SiO(C6H4-2-S)2]2 2- (II-1), [(VIVO(C6H5)PO(C6H4-2-S)2)2(MeO)]- (II-2). These two complexes have the [VO(μ-OR)2VO]2+ core unit in a syn-orthogonal arrangement and display ferromagnetic coupling interaction between vanadyl ions. We propose that this ferromagneric coupling interaction is likely due to the small dihedral angle between two basal planes, leading to the poor overlap of two dxy orbitals. In the last section, we obtained two multinuclear VIII/IV thiolate clusters, [V3Cl2{(CH3)Si(C6H4-2-S)3}3] (III-1) and [V4Cl{(CH3)Si(C6H4-2-S)3}4]- (III-2). In addition, we also got two vanadium thiolate compounds, [V{Si(CH3(5-Me- C6H4-2-S)CN)(5-Me-C6H4-2-S)2}2]-(III-3) and [V{SiO(5-Me- C6H4-2-S)3}]2 2- (III-4). In this dissertation, we detail the syntheses, structures, magnetic properties, electrochemical behavior and spectroscopic features of these complexes, as well as their significance.